Chlorination process



A. E. HOULEHAN. CHLORINATION PROCESS. APPLICATION FILED SEPT. 26. 1917.

1,358,851. Patented Nov. 16, 1920 Z SHEETS-SHEET I.

INVENTOR A. E. HOULEHAN.

CHLORINATION PROCESS. APPLICATION FILED SEPT- 26, m7-

1,358,85 1 Patented Nov. 16, 1920.

2 SHEETSSHET 2- IN VEN TOR Mina-l wll L -zxm ATTORNEYS T 0 all whom itmay concern UNITED STATES PATENT OFFICE.

ARTHUR EARL HOULEHAN, 0E WILMINGTON, DELAWARE, ASSIGNOR TO E. I. m;PON'I. DE NEMOURS AND COMPANY, OF WILMINGTON, DELAWARE, A CORPORATION OFDELAWARE":

CHLORINATION PROCESS.

Specification of Letters Patent.-

Patented Nov. 16, 1920.

Application filed September 26, 1917. Serial No. 193,260.

Be it known that I, ARTHUR E. HOULE- HAN, of Wilmington, in the countyof New Castle and in the State of Delaware, have invented a certain newand useful Improvement in Chlorination Processes, and. do

hereby declare that the following is a full,

clear, and exact description thereof.

My invention relates particularly to fa process for the chlorination ofsaturated hydrocarbons. It is applicable also to the chlorination ofmany other compounds, and is appl cable also to operation with the otherhalogens.

The object of my invention is to provide .a process by means of whichhalogenation, and particularly chlorination, may be brought abouteffectively. More particularly the object is to bring about thehalogenation or chlorination without depending upon the presence oflight, th-us obviating the disadvantages due to the application oflight, as for example, the variability and discontinuance of availablesunlight and necessity of using transparent containers. A further objectis to bring about such reaction by the application of heat. A furtherobject is to operate the invention in such a manner as to prevent lossof the materials handled, and so as to bring about complete halogenationor chlorination, or

up to the degree desired. Further objects of my invention will appearfrom the detailed description thereof contained here-' inafter.

While my invention is capable of being carried out in 'many difierentways, and many different ty .es of apparatus are capable of being use tocarry out my process, I have shown only onetype of apparatus in theaccompanying drawings, in which Figure 1 is an elevation of an apparatusmade in accordance with my invention, and

Fig. 2 is a plan view of the same. p

In the drawings, I have shown a main reservoir 1 adapted to be suppliedwith a quantity of naphtha through a valved fill-' ing pipe 2. Saidreservoir preferably also has a level indicating pipe 3. Petroleumnaphtha or the like may be pumped from the reservoir 1 by means of,e. avalved pipe 4, which preferably has a valved branch. pipe 5 leading to apump 6 which may be made of stoneware adapted to de-, liver into the topof, for example, an absorption tower -7, which may be filled withstoneware rings 8. In the construction shown the liquid passes down overthe stoneware rings 8 and meets an ascending current of chlorin, orother gaseous halogen, which may be supplied into the bottom of thetower by means of a pipe 9. The solution of the chlorin in the naphthamay be pumped from, for example, the bottom of the tower by means suchas a pipe 10 leading to a pump 11, which may be also made of stonewareand which may supply the liquid by means of a pipe 12 to, e. 9., heatingcoil 13, preferably also of stoneware. From the heating coil 13, theliquid may be delivered to a" cooling device such as coil 14, from whichit is discharged by means of a pipe 15 into thereservoir 1. A water pipe16, shown as having branches 17 and 18,

may supply water to two containers 19 and 20 in which coils 13 and 14cmay be carried; and a water outlet pipe 21 as shown having branches 22and 23, may convey away the water from the same. A steam supply pipe 24:may lead to thecontainer 19 in order to heat the water in the same. Thechlorination of the naphtha may be continued in this way by thecirculation of the same from the reservoir 1 through the tower 7, untilthe chlorination has been completed to the desired degree. Any vapors ofchlorin and naphtha which reach the top of the absorption tower 7 may beconveyed by means of a pipe 25 to the bottom of a condensing tower 26which mav contain stoneware rings 27. Any naphtha that is condensed. andany ducted by a pipe 30 to the bottom of a scrubbing tower 31. Thistower 31 may be suppliedwith a current of water, or the like,

from a reservoir 32 by meansof a pipe 33, a stoneware pump 34, and astoneware cooling coil 35 leading to the top of the tower 31. Theliquid-passing down through the tower 31 absorbs hydrochloric acidvapors from the ascending gases, and also causes some of the naphtha tobe condensed by reason of the cooling effect of the liquid. Liquid fromthe tower 31 may be returned to the tank 32by means of, e. g., a pipe36. In the operation of the embodiment described the solution ofhydrochloric acid thus obtained is circulated in this manner through thetank 32 and the tower 31 until it reaches the proper strength, and isthen withdrawn and replaced by a fresh body of water. Fresh water may beintroduced by means of a valved pipe 37 leading to, e. 9., a funnel 38,which may be connected to a trapped pipe 39, which may lead to the pipewhich enters the top of the tower 31 from the coil 35. Liquid may bedrawn off from the system through a valved pipe 40, which alsopreferably connects with the pipe located at the discharge end of thecoil 35. The tank 32 is furthermore preferably provided with a levelindicating pipe 41, and an overflow pipe 42 which may lead to the sewer.There may be also provided a pipe 43 to vent the top of the tank 32 tothe tower 31. Any naphtha which accumulates at the top of the tank 32may be withdrawn by, e. 9., a valved pipe 44 which may lead to the pipe5 and thence to the stoneware pump 6, so that it may be supplied to thetower 7. If desired, however, the naphtha may be withdrawn from the tank32 by means of a branch pipe 44 which may be connected to the pipe 44,and means such as a stoneware pump 44", which preferably has an outletpipe such as 44 provided with two branches, such as 44 and 44 which maybe arranged to convey the naphtha to, e. 9., the reservoir 1, or awayfrom the apparatus, as desired. Any vapors which reach the top of thetower 31 may be conveyed by a pipe, such as pipe 45, to the bottom of,e. 9., a chamber 46, which may have a plurality of trays 47 carryingslaked lime, so as to take up any chlor1n remaining in the as. Thevapors which reach the top of the c amber 46 may be conveyed by a pipe48 through the bottom of, e. 9., a scrubbing tower 49, which may besupphed with a downward current of, for enample, kerosene by any meanssuch as a pipe 50 which may lead from, c. 9., a stoneware pump 51, whichmay be supplied with kerosene, or the like, by a pipe, such pipe 52 froma tank 53, or the like. Said tank 53 1s preferably vented to the tower49 by a pipe 54. The kerosene, or the like, thus clrculated absorbs thelast traces of naphtha, and any gases which are not thus retained may beallowed to pass out to the atmosphere by, e. 9.,- valved pipe 55..

.reservoir 1. The heat applied in the coil 13 causes the chlorin to actupon the hydrocarbon, thus producing a 'chlor-hydrocarbon. Thechlorination is continued in this manner until it has reached thedesired degree of completion. During the chlorination, any vaporsescaping from the top of the absorption tower 7 are conveyed to thecondensing tower 26 in which naphtha is condensed from the gases, as isalso any chlor-hydrocarbons formed therein, so that the same may passdownwardly and back to the main naphtha reservoir 1. Any gases which arenot so condensed are then conveyed to the scrubbing tower 31 where theyare subjected to a current of water, so that the hydrochloric acid gasis recovered and additional naphtha vapors are condensed. The naphthavapors which accumulate in the form of a liquid are drawn off from timeto time and transferred to the absorption tower 7, and when thehydrochloric acid solution has reached the required strength, it isreplaced by a fresh body of water. The gases which escape from the topof the scrubbing tower are conveyed to the chamber 46 containing slakedlime, so that the chlorin in the gases may be recovered. The gases whichare not thus absorbed are finally conveyed to the scrubbing tower 49,

where the remainder of the naphtha is re-' covered by solution in thecurrent of kerosene, or the like, which is circulated through thistower.

In this way the naphtha becomes chlorinated to the desired degree, andany gases escaping during the process are recovered so as; to avoid lossof the same. I

"While I have described my invention above in detail, I wish it to beunderstood,

that many changes may be made therein without departing from the spiritthereof.

F urthermore', wherever I have used the term chlorin, or referred tochlorina-' tion, I wish it to be understood that I thereby mean toinclude the other halogens, and halogenation in general.

I claim: p

1. The process which comprises absorbing chlorin in a hydrocarbon liquidin the absence of light, and then heating the liquid to bring about itschlorination.

2. The process which comprises absorbing ing chlorin in naphtha in theabsence of light, and then heating the naphtha to bring 10 about itschlorination.

In testimony that I claim the foregoing I have hereunto'set my hand.

ARTHUR EARL 'HOULEHAN.

Witnesses:

CHAS. E. WEBB, Jr., EDWARD BERNHARDT.

